Dielectric ceramic, laminated ceramic capacitor, method for producing the dielectric ceramic, and method for manufacturing the multilayer ceramic capacitor

ABSTRACT

Provided is a laminated ceramic capacitor which produces excellent lifetime characteristics in a high-temperature loading test even when dielectric layers are reduced in thickness. The dielectric ceramic contains, as its main constituent, a compound represented by the general formula (Ba 1-x-y Ca x Re y )(Ti 1-z M z )O 3  (where Re is at least one or more elements selected from among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y, and M is at least one or more elements selected from among Mg, Mn, Al, Cr, and Zn), 0≦x≦0.2, 0.002≦y≦0.1, and 0.001≦z≦0.05. This dielectric ceramic has crystal grains of 20 nm or more and 150 nm or less in average grain size.

This is a continuation of application Ser. No. PCT/JP2011/068942, filedAug. 23, 2011, the entire contents of which are incorporated herein byreference.

TECHNICAL FIELD

The present invention relates to a dielectric ceramic and a method forproducing the dielectric ceramic. In addition, the present inventionrelates to a laminated ceramic capacitor configured with the use of thedielectric ceramic, and a method for manufacturing the laminated ceramiccapacitor.

BACKGROUND ART

With the progress in recent electronics technology, a reduction in sizeand increase in capacitance have been required for laminated ceramiccapacitors. In order to satisfy these requirements, a reduction indielectric layer thickness has advanced in the layers of laminatedceramic capacitors. However, the reduction of the dielectric layers inlayer thickness causes an increase in the electric field intensityapplied per layer. Therefore, improvements in reliability in the case ofapplying a voltage, and in particular, improvements in the lifetimecharacteristic in a high-temperature loading test is required for thedielectric ceramic used in the dielectric layers.

For example, Patent Document 1 discloses a dielectric ceramic which ischaracterized in that the dielectric ceramic has a perovskite-typecrystal structure containing barium titanate as its main constituent andcontaining a rare-earth element, magnesium, and manganese as accessoryconstituents, and is represented by the composition formula(Ba_(1-y)RE_(y))(Ti_(1-a-b)M_(ao)Mn_(b))O₃ (RE: rare-earth element),with respective ranges expressed by 0.06≦y≦0.09, 0.03≦ao≦0.045, and0.012≦b≦0.018.

PRIOR ART DOCUMENT Patent Document

-   Patent Document 1: JP 2007-145649 A

DISCLOSURE OF THE INVENTION Problem to be solved by the invention

Patent Document 1 fails to disclose any case of reduction of dielectriclayers in thickness. Therefore, it is not known whether or not thedielectric ceramic described in Patent Document 1 has high reliabilityin the case of applying a voltage when dielectric layers are reduced inthickness down to on the order of 1 μm.

The present invention has been achieved in view of the problem, and anobject of the present invention is to provide a laminated ceramiccapacitor which has a favorable dielectric property and producesexcellent lifetime characteristics in a high-temperature loading test,even when a voltage with a high electric field intensity is applied todielectric layers further reduced in thickness.

Means for Solving the Problem

A dielectric ceramic according to the present invention contains, as itsmain constituent, a compound represented by the general formula(Ba_(1-x-y)Ca_(x)Re_(y))(Ti_(1-z)M_(z))O₃ (where Re is at least one ormore elements selected from among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, and Y, and M is at least one or more elementsselected from among Mg, Mn, Al, Cr, and Zn) in the range of 0≦x≦0.2,0.002≦y≦0.1, and 0.001≦z≦0.05, and has crystal grains of 20 nm or moreand 150 nm or less in average grain size.

In addition, the dielectric ceramic according to the present inventionpreferably has an average grain size of 20 nm or more and less than 100nm.

In addition, the present invention is directed to a laminated ceramiccapacitor which includes: a laminated body including a plurality ofstacked dielectric layers and a plurality of internal electrodes formedalong interface between dielectric layers; and a plurality of externalelectrodes formed on the outer surface of the laminated body andelectrically connected to the internal electrodes, and the laminatedceramic capacitor is characterized in that the dielectric layers arecomposed of the dielectric ceramic.

Further, the present invention is also directed to a method forproducing a dielectric ceramic, which includes the steps of: preparing aceramic powder containing, as its main constituent, a compoundrepresented by the general formula(Ba_(1-x-y)Ca_(x)Re_(y))(Ti_(1-z)M_(z))O₃ (where Re is at least one ormore elements selected from among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, and Y, and M is at least one or more elementsselected from among Mg, Mn, Al, Cr, and Zn) in the range of 0≦x≦0.2,0.002≦y≦0.1, and 0.001≦z≦0.05; forming the ceramic powder into acompact; and firing the compact to obtain a dielectric ceramic includingcrystal grains of 20 nm or more and 150 nm or less in average grainsize.

In the method for producing a dielectric ceramic according to thepresent invention, the average grain size is preferably 20 nm or moreand less than 100 nm.

In addition, the present invention is also directed to a method formanufacturing a laminated ceramic capacitor, which is characterized byincluding the method for producing a dielectric ceramic.

Advantageous Effect of the Invention

The dielectric ceramic according to this invention has the compositionas described above, as well as crystal grains defined in terms of grainsize as described above, thereby making it possible to provide alaminated ceramic capacitor which has a favorable dielectric propertyand produces excellent lifetime characteristics in a high-temperatureloading test, even when a voltage with a high electric field intensityis applied to dielectric layers further reduced in thickness.

BRIEF EXPLANATION OF DRAWINGS

FIG. 1 is a cross-sectional view of a laminated ceramic capacitoraccording to the present invention.

DESCRIPTION OF THE INVENTION

An embodiment for carrying out the present invention will be describedbelow.

FIG. 1 is a cross-sectional view of a laminated ceramic capacitoraccording to the present invention.

The laminated ceramic capacitor 1 includes a laminated body 5. Thelaminated body 5 includes a plurality of stacked dielectric layers 2,and a plurality of internal electrodes 3 and 4 formed along interfacesbetween dielectric layers 2. Materials for the internal electrodes 3 and4 include, for example, a material containing Ni as its mainconstituent.

External electrodes 6 and 7 are formed in different positions on theouter surface of the laminated body 5. Materials for the externalelectrodes 6 and 7 include, for example, a material containing Ag or Cuas its main constituent. In the laminated ceramic capacitor embodimentshown in FIG. 1, the external electrodes 6 and 7 are formed onrespective end surfaces of the laminated body 5, which are opposed toeach other. The internal electrodes 3 and 4 are electrically connectedrespectively to the external electrodes 6 and 7. Furthermore, theinternal electrodes 3 and 4 are stacked alternately with the dielectriclayers 2 interposed therebetween in the laminated body 5.

It is to be noted that the laminated ceramic capacitor 1 may be atwo-terminal capacitor including two external electrodes 6 and 7, or maybe a multi-terminal capacitor including a larger number of externalelectrodes.

The dielectric layers 2 are composed of a dielectric ceramic containing,as its main constituent, a compound represented by the general formula(Ba_(1-x-y)Ca_(x)Re_(y))(Ti_(1-z)M_(z))O₃ (where Re is at least one ormore elements selected from among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, and Y, and M is at least one or more elementsselected from among Mg, Mn, Al, Cr, and Zn) and where 0≦x≦0.2,0.002≦y≦0.1, and 0.001≦z≦0.05. Furthermore, the dielectric ceramic isadapted to have crystal grains of 20 nm or more and 150 nm or less inaverage grain size.

When the average grain size is 20 nm or more and less than 100 nm, it ispossible to provide a laminated ceramic capacitor which produces furtherexcellent lifetime characteristics in a high-temperature loading test.

It is to be noted that the molar ratio between (Ba, Ca, Re) and (Ti, M)is set appropriately, and preferably selected in the range of 0.98 to1.05.

The ceramic powder is prepared, for example, by a solid-phase synthesismethod. Specifically, first, compound powders such as oxides,carbonates, chlorides, and metal organic compounds, each including Ba,Ca, Re, Ti, or M as a constituent element for the main constituent, aremixed in predetermined proportions, and subjected to calcination. It isto be noted that a hydrothermal synthesis method, a hydrolysis method,etc. may be applied in addition to the solid-phase synthesis method.

The laminated ceramic capacitor is, for example, manufactured asfollows. The ceramic powder obtained in the way described above is usedto prepare ceramic slurry. Then, ceramic green sheets are formed by asheet forming method or the like. A plurality of stacked ceramic greensheets is subjected to pressure bonding to obtain a compact, and thecompact is subjected to firing. In this firing step, the ceramic powderprovides dielectric layers composed of the dielectric ceramic.Thereafter, external electrodes are formed by baking or the like on endsurfaces of the laminated body.

Next, experimental examples will be described which were carried outaccording to the present invention.

Experimental Example 1 (A) Preparation of Ceramic Powder

Respective powders of particulate BaCO₃, CaCO₃, TiO₂, Re (Re is La, Ce,Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y), and M (M is Mg,Mn, Al, Cr and Zn) were prepared as starting raw materials. Respectivepowders of La₂O₃, Ce₂O₃, Pr₂O₃, Nd₂O₃, Sm₂O₃, Eu₂O₃, Gd₂O₃, Tb₂O₃,Dy₂O₃, Ho₂O₃, Er₂O₃, Tm₂O₃, Yb₂O₃, Lu₂O₃, and Y₂O₃ were prepared as theRe powder. In addition, respective powders of MgCO₃, MnCO₃, Al₂O₃,Cr₂O₃, and ZnO were prepared as the M powder. Then, these powders wereweighed for the composition of (Ba_(1-x-y)Ca_(x)Re_(y))(Ti_(1-z)M_(z))O₃in Table 1, and then mixed for 80 hours in a ball mill. Thereafter, themixed powders were subjected to a heat treatment at 1000° C. forcalcination synthesis, thereby providing a main constituent powder ofthe formula (Ba_(1-x-y)Ca_(x)Re_(y))(Ti_(1-z)M_(z))O₃. Thereafter, 1.5parts by mol of BaCO₃ and 2 parts by mol of SiO₂ were added to 100 partsby mol of the main constituent powder to obtain a ceramic powder.

The obtained ceramic powder had an average grain size on the order of 10nm. In addition, XRD indicated that unreacted materials in the ceramicpowder were below the detection level. More specifically, it has beenconfirmed that this ceramic powder is a highly synthesized powder, inspite of being extremely fine grains.

TABLE 1 Molar Ratio Sample Ca Re (Ba, Ca, Number Re M Content x Contentx M Content z Re)/(Ti, M) 1 Gd Mn 0 0.05 0.025 0.995 2 La Mg 0.197 0.040.02 0.996 3 Ce Al 0.05 0.002 0.002 1.006 4 Pr Cr 0.05 0.1 0.045 0.993 5Nd Zn 0.05 0.005 0.001 1.000 6 Dy Mg 0.05 0.07 0.05 0.986 7 Sm Mg 0.050.06 0.03 1.005 8 Er Mg 0.1 0.04 0.02 1.002 9 Lu Mn 0.1 0.09 0.045 1.00410 Ho Al 0 0.08 0.04 0.995 11 Eu Zn 0.1 0.05 0.025 1.005 12 Gd Mg 0.060.04 0.02 0.999 13 Tm Mg 0.075 0.03 0.015 1.006 14 Tb Mn 0 0.03 0.0151.001 15 Y Mg 0.05 0.06 0.03 1.004 16 Dy Mn 0.05 0.08 0.04 0.987 17 YbMg 0.05 0.06 0.03 0.991 18 Yb Al 0.05 0.04 0.02 1.002 19 Tm Mn 0.05 0.030.015 1.001 20 Eu Al 0.21 0.04 0.02 1.009 21 Pr Mn 0.05 0.001 0.0051.000 22 Ho Zn 0.05 0.115 0.045 1.005 23 Er Al 0.05 0.005 0.0005 0.99424 Y Mg 0.05 0.091 0.072 1.001

(B) Preparation of Laminated Ceramic Capacitor

First, ceramic green sheets to serve as dielectric layers were formed.Specifically, the ceramic powder described above, a polyvinyl butyralbased binder and ethanol combination was subjected to wet mixing for 24hours in a ball mill. Thereafter, filtering was carried out with the useof a filter to prepare slurry by eliminating the powder of the grainsizes other than grain sizes in a predetermined range. Then, this slurrywas formed into sheets by a RIP method to obtain ceramic green sheets.The ceramic green sheets were adapted to have the thickness after firingshown in “Dielectric Layer Thickness” in Table 2 as will be describedlater.

Next, a compact was prepared. Specifically, a conductive pastecontaining Ni as its main constituent was applied by screen printingonto specific ceramic green sheets to form conductive paste films toserve as internal electrodes. Then, the plurality of ceramic greensheets with the conductive paste films formed thereon was stacked so asto alternate the sides to which the conductive paste films wereextracted, and then subjected to pressure bonding to obtain the compact.

Next, the compact was subjected to firing. Specifically, first, thebinder was burned by heating to a temperature of 300° C. in a reducingatmosphere. Thereafter, firing was carried out at a temperature of 1200°C. for 1 hour in a reducing atmosphere composed of a H₂—N₂—H₂O gas withan oxygen partial pressure of 10⁻¹⁰ MPa.

Next, external electrodes were formed. Specifically, a Cu pastecontaining a B₂O₃—Li₂O−SiO₂—BaO based glass frit was applied onto bothend surfaces of the laminated body. Thereafter, the Cu paste was bakedby heating at a temperature of 800° C. in a nitrogen atmosphere. In thisway, external electrodes were formed which were electrically connectedto the internal electrodes.

The laminated ceramic capacitor was prepared in the way described above.The laminated ceramic capacitor had external dimensions of length: 1.0mm, width: 0.5 mm, and thickness: 0.5 mm, the number of effectivedielectric layers was 100, and the area of the internal electrodeopposed per dielectric layer was 0.3 mm². In addition, the dielectriclayer interposed between the internal electrodes had a thickness asshown in the “Dielectric Layer Thickness” of Table 2.

(C) Characterization

The laminated ceramic capacitors obtained were evaluated for varioustypes of characteristics.

Average Grain Size

The average grain size was calculated as follows. First, the laminatedceramic capacitors for each sample were fractured, and subjected tothermal etching at a temperature of 1000° C., and the fractured surfaceswere observed with the use of a scanning microscope. Then, the observedimages were subjected to an image analysis to measure the grain sizes ofthe crystal grains with the equivalent circle diameters of the crystalgrains as the grain sizes. Then, for each sample, the grain sizes ofthree-hundred crystal grains were measured to calculate the averagevalue as an average grain size.

High-Temperature Loading Life Test

The high-temperature loading life test was carried out as follows. DCvoltages were applied to the laminated ceramic capacitors according toeach sample to produce each electric field intensity of 6.3 kV/mm and12.6 kV/mm at a temperature of 125° C. Then, the high-temperatureloading life test was carried out for one hundred samples to determine,as defectives, the samples having an insulation resistance value of 100kΩ or less before a lapse of 1000 hours, and to find the number ofdefectives among the hundred samples.

Table 2 shows the average grain size, the dielectric layer thickness,and the number of defectives after the high-temperature loading lifetest.

TABLE 2 Average Dielectric Number of Defectives in High- Sample GrainSize Layer Temperature Loading Life Test Number [μm] Thickness [μm] 6.3V/μm 12.6 V/μm 1 85 0.87 0/100 0/100 2 78 0.78 0/100 0/100 3 55 0.560/100 0/100 4 132 0.98 0/100 3/100 5 24 0.48 0/100 0/100 6 128 1.050/100 3/100 7 64 0.42 0/100 0/100 8 57 0.32 0/100 0/100 9 141 1.02 0/1004/100 10 35 0.61 0/100 0/100 11 81 0.72 0/100 0/100 12 48 0.35 0/1000/100 13 31 0.82 0/100 0/100 14 98 1.01 0/100 0/100 15 108 1.23 0/1003/100 16 28 0.55 0/100 0/100 17 148 1.30 0/100 6/100 *18 18 0.34 72/100 87/100  *19 167 0.82 100/100  100/100  *20 110 0.81 68/100  84/100  *21145 0.75 100/100  100/100  *22 48 0.85 75/100  88/100  *23 98 0.6597/100  100/100  *24 69 1.02 68/100  81/100 

It is to be noted that the sample numbers marked with * in Tables 1 and2 refer to samples which fall outside the scope of the presentinvention.

(D) Consideration

Sample numbers 1, 10, and 14 containing a dielectric (Ba, Re) (Ti, M)O₃as their main constituent exhibited favorable reliability at the DCvoltages of both 6.3 kV/μm and 12.6 kV/μm. In addition, sample numbers 2to 9, 11 to 13, and 15 to 17 containing (Ba, Ca, Re) (Ti, M)O₃ as theirmain constituent exhibited favorable reliability at the DC voltages ofboth 6.3 kV/μm and 12.6 kV/μm. Further, sample numbers 1 to 3, 5, 7, 8,10 to 14, having 16 of 20 nm or more and less than 100 nm in averagegrain size exhibited favorable reliability without causing anydefectives even under the test condition at the DC voltage of 12.6kV/μm.

In contrast to these samples, sample number 18 having less than 20 nm inaverage grain size yielded a result of low reliability. In addition,sample number 19 having more than 150 nm in average grain size yielded aresult of low reliability. This is considered to be because the largeaverage grain size caused the electric field to be concentrated locallyin the laminated body in the case of sample number 19.

Sample number 20 also yielded a result of low reliability. This isconsidered to be because the Ca content x more than 0.02 madedensification less likely to degrade the mechanical strength.

Sample number 21 with the Re content y less than 0.002 yielded a resultof low reliability. In addition, sample number 22 also yielded a resultof low reliability. This is considered to be because the Re content ymore than 0.1 caused segregation after the firing.

Sample number 23 with the M content z less than 0.001 yielded a resultof low reliability. In addition, sample number 24 also yielded a resultof low reliability. This is considered to be because the M content zmore than 0.05 caused segregation after the firing.

Experimental Example 2

The influence of impurities was evaluated in Experimental Example 2.There is a possibility that Sr, Zr, Hf, Zn, Na, Ag, Pd, Ni, and the likewill be present as impurities in a raw material preparation step, etc.for the laminated ceramic capacitor. These have the possibility of beingpresent in the crystal grains and at crystal grain boundaries betweencrystal grains. In addition, there is a possibility that an internalelectrode constituent will be diffused into crystal grain boundaries inthe dielectric ceramic and crystal grain boundaries between crystalgrains in a firing step, etc. for the laminated ceramic capacitor.Experimental Example 2 is intended to evaluate the influence of theseimpurities.

(A) Preparation of Ceramic Powder

Ceramic powders were prepared in the same way as in Experimental Example1, except that the impurity components shown in Table 3 were added tothe composition of sample number 13 in Experimental Example 1.

TABLE 3 Sample Number Details of Impurity Components 31 0.4Hf, 0.02Zn 320.25Sr, 0.1Na 33 0.5Zr, 0.02Ag, 0.01Ni 34 0.05Ni, 0.1Na 35 0.2Na, 0.02Hf36 0.4Pd, 3.2Ni 37 1.1Ag, 1.0Zr 38 0.1Pd, 0.05Sr 39 0.003Ag, 0.05Pd 401.3Ni(B) Preparation of Laminated Ceramic Capacitor

The ceramic powders were used to prepare laminated ceramic capacitors inthe same way as in Experimental Example 1.

(C) Characterization

The laminated ceramic capacitors obtained were evaluated for varioustypes of characteristics in the same way as in Experimental Example 1.Table 4 shows the results of a high-temperature loading life test.

TABLE 4 Number of Defectives in High- Sample Temperature Loading LifeTest Number 6.3 V/μm 12.6 V/μm 31 0/100 0/100 32 0/100 0/100 33 0/1000/100 34 0/100 0/100 35 0/100 0/100 36 0/100 0/100 37 0/100 0/100 380/100 0/100 39 0/100 0/100 40 0/100 0/100(D) Consideration

As can be seen from Table 4, each of samples 31 to 40 with theimpurities contained therein exhibits high reliability, which resultsfrom that fact that the number of defectives in the high-temperatureloading life test is 0 at the electric field intensities of both 6.3kV/mm and 12.6 kV/mm. In addition, the average grain size was 20 nm ormore and 150 nm or less in each case of samples 31 to 40.

DESCRIPTION OF REFERENCE SYMBOLS

-   -   1 laminated ceramic capacitor    -   2 dielectric layer    -   3, 4 internal electrode    -   5 laminated body    -   6, 7 external electrode

The invention claimed is:
 1. A dielectric ceramic comprising, as itsmain constituent, a compound represented by the general formula(Ba_(1-x-y)Ca_(x)Re_(y))(Ti_(1-z)M_(z))O₃ in which Re is at least oneelement selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu,Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y, and M is at least one elementselected from the group consisting of Mg, Mn, Al, Cr, and Zn, 0≦x≦0.2,0.002≦y≦0.1, and 0.001≦z≦0.05, and having crystal grains of 20 nm ormore and 150 nm or less in average grain size.
 2. The dielectric ceramicaccording to claim 1, wherein the average grain size is 20 nm or moreand less than 100 nm.
 3. The dielectric ceramic according to claim 2,wherein 0.004≦y, and 0.0015≦z≦0.04.
 4. The dielectric ceramic accordingto claim 3, wherein x is
 0. 5. The dielectric ceramic according to claim3, wherein x is greater than
 0. 6. A laminated ceramic capacitorcomprising: a laminated body including a plurality of stacked dielectriclayers and a plurality of internal electrodes disposed at interfacesbetween dielectric layers; and a plurality of external electrodes on anouter surface of the laminated body and electrically connected to theinternal electrodes, wherein the dielectric layers are composed of thedielectric ceramic according to claim
 3. 7. A laminated ceramiccapacitor comprising: a laminated body including a plurality of stackeddielectric layers and a plurality of internal electrodes disposed atinterfaces between dielectric layers; and a plurality of externalelectrodes on an outer surface of the laminated body and electricallyconnected to the internal electrodes, wherein the dielectric layers arecomposed of the dielectric ceramic according to claim
 2. 8. A laminatedceramic capacitor comprising: a laminated body including a plurality ofstacked dielectric layers and a plurality of internal electrodesdisposed at interfaces between dielectric layers; and a plurality ofexternal electrodes on an outer surface of the laminated body andelectrically connected to the internal electrodes, wherein thedielectric layers are composed of the dielectric ceramic according toclaim
 1. 9. A method for producing a dielectric ceramic, the methodcomprising: providing a compact containing a ceramic powder containing,as its main constituent, a compound represented by the general formula(Ba_(1-x-y)Ca_(x)Re_(y))(Ti_(1-z)M_(z))O₃ in which Re is at least oneelement selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu,Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y, and M is at least one elementselected from the group consisting of Mg, Mn, Al, Cr, and Zn, 0≦x≦0.2,0.002≦y≦0.1, and 0.001≦z≦0.05; and firing the compact to obtain adielectric ceramic including crystal grains of 20 nm or more and 150 nmor less in average grain size.
 10. The method for producing a dielectricceramic according to claim 9, wherein the average grain size is 20 nm ormore and less than 100 nm.
 11. The method for producing a dielectricceramic according to claim 10, wherein 0.004≦y, and 0.0015≦z≦0.04. 12.The method for producing a dielectric ceramic according to claim 11,wherein x is
 0. 13. The method for producing a dielectric ceramicaccording to claim 11, wherein x is greater than
 0. 14. The method forproducing a dielectric ceramic according to claim 9, further comprisingforming the compact.
 15. The method for producing a dielectric ceramicaccording to claim 14, further comprising forming the ceramic powder.16. A method for manufacturing a laminated ceramic capacitor, whereinthe method comprises the method for producing a dielectric ceramicaccording to claim
 3. 17. A method for manufacturing a laminated ceramiccapacitor, wherein the method comprises the method for producing adielectric ceramic according to claim
 2. 18. A method for manufacturinga laminated ceramic capacitor, wherein the method comprises the methodfor producing a dielectric ceramic according to claim
 1. 19. A methodfor manufacturing a laminated ceramic capacitor, wherein the methodcomprises the method for producing a dielectric ceramic according toclaim
 9. 20. A method for manufacturing a laminated ceramic capacitor,wherein the method comprises the method for producing a dielectricceramic according to claim 10.